TW201920484A - Polyimide precursor composition, polyimide film prepared using same, transparent polyimide substrate for oxide TFT, and transparent polyimide substrate for LTPS - Google Patents

Abstract

The polyimide precursor composition according to the present invention uses a siloxane-based diamine having a specific structure and a solvent having a positive partition-coefficient, thereby alleviating the thermal expansion-shrinkage characteristics of the resulting polyimide film and providing excellent transparency, heat resistance, mechanical strength and flexibility, while effectively reducing residual stress. Accordingly, it can be effectively used as a substrate for a device, a cover substrate for a display, an optical film, an IC (integrated circuit) package, an adhesive film, a multilayer flexible printed circuit (FPC), a tape, a touch panel, protective films for optical discs, and the like.

Description

Polyimide precursor composition and polyimide film prepared using the same

This application claims the benefit of priority based on Korean Patent Application No. 10-2017-0117989, filed on September 14, 2017. This specification includes all of the contents disclosed in the documents of the aforementioned Korean patent application as a part .

The invention provides a polyimide precursor composition for preparing a low-phase-difference, high-heat-resistant polyimide film that can ease thermal expansion-contraction behavior.

Polyimide (PI), as a polymer with relatively low crystallinity or mostly having an amorphous structure, is not only easy to synthesize, but can be made into a thin film without using a crosslinking group for hardening. Polymer materials with advantages such as transparency, excellent heat resistance and chemical resistance due to strong chain structure, excellent mechanical properties, electrical properties, and dimensional stability, are currently widely used in the automotive and aerospace fields , Flexible circuit substrates, liquid crystal alignment films for liquid crystal display (LCD) liquid crystal alignment films, adhesives and coating materials, and other electrical and electronic materials.

However, even if polyimide is a high-performance polymer material with high thermal stability, mechanical properties, chemical resistance, and electrical properties, it still fails to meet the basic necessary conditions required in the display field, that is, colorless and transparent properties. And, there is a problem that the coefficient of thermal expansion needs to be further reduced. For example, the thermal expansion coefficient of Kapton sold by DuPont is about 30 ppm / ° C. Although it shows a low thermal expansion coefficient value, it still cannot meet the requirements of plastic substrates. Therefore, more current researches are focused on maintaining the basic properties of polyimide and minimizing changes in its optical and thermal properties.

Generally, taking aromatic polyfluorene imine as an example, it has a dark brown inherent color, and can carry out charge transfer complex by the π electrons of benzene existing in the fluorene imine main chain due to the inter-chain bonding. (Also known as CT-complex), and the reason for the above-mentioned charge transfer recombination is that there are σ electrons, π electrons, and nonbonding non-covalent electron pairs in the imide structure, so electron excitation occurs. .

A typical polyimide absorbs light from a wavelength below 400 nm in the visible light region between 500 nm, and thus exhibits a color corresponding to the above light (ie, yellow to red). Therefore, in order to reduce the shortcomings of aromatic polyfluorene imines (that is, charge transfer complexes), it is possible to introduce trifluoromethyl (-CF ₃ ), fluorene (-SO ₂ ), A method in which relatively negative anion elements such as ether (-O-) are used to limit the movement of π electrons to reduce the resonance effect. Furthermore, an olefinic cyclic (cycloolefin) structure other than benzene can be introduced. The density of the π electrons existing in the main chain is reduced to produce a colorless and transparent polyfluorene film.

On the other hand, polyamidamine and imine have excellent properties such as heat resistance, mechanical strength, and electrical characteristics. Therefore, they have been widely used as industrial materials in the electrical, electronic, mechanical, and aerospace fields for a long time. In addition, the structure of polyimide is different from that of typical polyimide. It is known to be soluble in organic solvents, so it is also used as an essential solution for enamel varnish, coating agents for electrical insulation, and coatings. Forming uses.

However, in order to be used in the display field, it is still necessary to develop a polymer for a flexible display that has a lower thermal expansion coefficient and higher solubility, transparency, and thermal stability.

Problems to be Solved by the Invention

The problem to be solved by the present invention is to provide a polyimide precursor composition for preparing a low polyimide film with low phase difference and high heat resistance, which can ease thermal expansion-contraction behavior.

Another problem to be solved by the present invention is to provide a polyimide film prepared from the polyimide precursor composition.

Another object of the present invention is to provide a display element using the polyfluoreneimide film.

Means of solving the problem

In order to solve the above technical problems, the present invention provides a polyfluorene imide precursor composition containing an acid dianhydride, a diamine, and dimethylsiloxane (DMS) -diphenylsiloxane represented by the following structural formula. (DPS) An oligomer and a solvent having a positive partition coefficient (LogP) at 25 ° C and a density of 1 g / cm ³ or less were used as polymerization components.

In the above structural formula, p and q are mole fractions. When p + q = 100, p is 70 to 90, and q is 10 to 30.

According to a preferred embodiment, the solvent may be an amidine solvent, specifically one selected from dimethylpropanamide (DMPA) or diethylpropanamide (DEPA).

According to an embodiment, the molecular weight of the dimethyl siloxane (DMS) -diphenyl siloxane (DPS) oligomer may be 4,000 g / mol or more.

According to an embodiment, the acid dianhydride may be one selected from a tetracarboxylic dianhydride having a tetravalent organic group structure including the following Chemical Formula 2a to Chemical Formula 2h. [Chemical Formula 2a] [Chemical Formula 2b] [Chemical Formula 2c] [Chemical Formula 2d] [Chemical Formula 2e] [Chemical Formula 2f] [Chemical Formula 2g] [Chemical Formula 2h]

In the above Chemical Formulas 2a to 2h, the above R ₁₁ to R ₂₄ may be each independently selected from a halogen atom including -F, -Cl, -Br, and -I, a hydroxyl group (-OH), and a thiol group (-SH ), Nitro (-NO ₂ ), cyano, alkyl having 1 to 10 carbon atoms, haloalkoxy having 1 to 4 carbon atoms, haloalkyl having 1 to 10 carbon atoms, carbon number Is a substituent in an aryl group of 6 to 20, the above a1 may be an integer of 0 to 2, a2 is an integer of 0 to 4, a3 is an integer of 0 to 8, and a4 and a5 are each independently an integer of 0 to 3 , A7 and a8 are independently integers from 0 to 3, a10 and a12 are independently integers from 0 to 3, a11 is an integer from 0 to 4, a15 and a16 are independently integers from 0 to 4, a17 and a16 are independently a18 is independently an integer from 0 to 4, a6, a9, a13, a14, a19, a20 are each independently an integer from 0 to 3, n is an integer from 1 to 3, and A ₁₁ to A ₁₆ may be independently Selected from -O-, -CR'R "-, -C (= O)-, -C (= O) O-, -C (= O) NH-, -S-, -SO _2- , benzene One of the groups consisting of a radical and a combination thereof, wherein the R 'and R "are each independently selected from the group consisting of a hydrogen atom and a carbon number of 1 to 10 One of the groups consisting of an alkyl group and a fluoroalkyl group having 1 to 10 carbon atoms.

According to an embodiment, the content of the overall diamine may include a diamine having a structure of the following Chemical Formula 3 from 80 mol% to 99 mol%. [Chemical Formula 3]

In the above Chemical Formula 3, the R ₃₁ and R ₃₂ are each independently selected from a halogen atom including -F, -Cl, -Br, and -I, a hydroxyl group (-OH), a thiol group (-SH), and a nitro group. (-NO ₂ ), cyano, alkyl having 1 to 10 carbon atoms, haloalkoxy having 1 to 4 carbon atoms, haloalkyl having 1 to 10 carbon atoms, and 6 to 20 carbon atoms A substituent in the aryl group of Q, Q may be selected from a single bond, -O-, -CR'R "-, -C (= O)-, -C (= O) O-, -C (= O) One of the groups consisting of NH-, -S-, -SO _2- , phenylene, and combinations thereof. At this time, the above R 'and R "are independently selected from the group consisting of a hydrogen atom and a carbon number of 1 to One of the groups consisting of an alkyl group having 10 carbon atoms and a fluoroalkyl group having 1 to 10 carbon atoms.

According to an embodiment, the total tetracarboxylic dianhydride may include 20 mol% to 80 mol% of a tetracarboxylic dianhydride including the following Chemical Formula 4. [Chemical Formula 4]

According to an embodiment, the tetracarboxylic dianhydride of the following chemical formula 5 may be included in the overall tetracarboxylic dianhydride in an amount of 20 mol% to 80 mol%. [Chemical Formula 5]

In the above Chemical Formula 5, Q ₁ and Q ₂ are each independently selected from a single bond, -O-, -C (= O)-, -C (= O) O-, -C (= O) NH-, One of the groups consisting of -S-, -SO _2- , phenylene, and combinations thereof.

According to an embodiment, the tetracarboxylic dianhydride of the following Chemical Formula 4 and Chemical Formula 5 may be included together. [Chemical Formula 4] [Chemical Formula 5]

In the above Chemical Formula 5, Q ₁ and Q ₂ are each independently selected from a single bond, -O-, -C (= O)-, -C (= O) O-, -C (= O) NH-, One of the groups consisting of -S-, -SO _2- , phenylene, and combinations thereof.

In order to solve another problem of the present invention, a polyimide film prepared from the copolymer of polyimide is provided.

According to an embodiment, the haze of the polyfluoreneimide film may be 2 or less.

According to an embodiment, the glass transition temperature (Tg) of the polyfluoreneimide film may be 350 ° C. or higher.

According to an embodiment, the coefficient of thermal expansion (CTE) of the polyfluoreneimide film may be 100 ppm / ° C or lower.

Furthermore, the present invention provides a transparent polyfluorene for oxide thin film transistor (TFT) or low temperature polycrystalline silicon (LTPS) prepared from the copolymer of polyfluorene imide. Amine substrate.

Invention effect

According to the present invention, a polyfluorene imide prepared by polymerizing and curing a polymerization component including a diamine (DMS-DPS) containing a high molecular weight siloxane structure in the presence of an organic solvent having a positive partition coefficient (LogP) In the copolymer, DMS-DPS has a nano-sized continuous phase distribution, so that it can maintain heat resistance and mechanical properties, and effectively reduce residual stress, so it is suitable for polymer materials with high heat resistance and low stress. . Therefore, it can be used for, for example, a substrate for a device, a cover substrate for a display, an optical film, an integrated circuit (IC) package, an adhesive film, and a multilayer flexible printed circuit (FPC). , Tape, touch panel, protective film for optical discs, etc.

The present invention can implement various transformations, and can have various embodiments. Specific embodiments are shown in the drawings and described in detail in the detailed description. However, the above-mentioned embodiments are not intended to limit the present invention to specific implementations, and should be understood to include all changes, equivalents, or alternatives included in the scope of the idea and technology of the present invention. When the present invention is described, when it is judged that the specific description of the related known technology may confuse the gist of the present invention, the detailed description thereof is omitted.

In this specification, unless otherwise mentioned, all compounds or organic groups may be substituted or unsubstituted. Here, "substituted" means that at least one hydrogen included in a compound or an organic group is selected from the group consisting of a halogen atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group, and 3 to 30 carbon atoms. Cycloalkyl, aryl having 6 to 30 carbons, hydroxyl, alkoxy having 1 to 10 carbons, carboxylic acid, aldehyde, epoxy, cyano, nitro, amine, sulfo Substitutes in groups consisting of acid groups and their derivatives.

Furthermore, in this specification, unless specifically mentioned, "a combination thereof" refers to two or more functional groups through, for example, a single bond, a double bond, a triple bond, and an alkylene group having 1 to 10 carbon atoms. (For example, methylene (-CH _2- ), ethylene (-CH ₂ CH _2- ), etc.), fluoroalkylene having 1 to 10 carbon atoms (for example, fluoromethylene (-CF ₂ -), Perfluoroethylene (-CF ₂ CF _2- ), etc.), heteroatoms such as N, O, P, S or Si or functional groups including them (for example, including a carbonyl group in the molecule (-C = O-), ether group (-O-), ester group (-COO-), -S-, -NH- or -N = N- and other heteroalkylene groups), or two The above functional groups are condensed or linked.

Flexible devices with high-temperature processes require heat resistance at high temperatures, especially organic light emitting diodes (OLEDs) using oxide thin film transistors (TFTs) and low temperature polycrystalline silicon (LTPS) processes. In the case of diode (OLED) devices, the process temperature is above 350 ° C, or even close to 500 ° C.

At this temperature, even if it is a polyimide having excellent heat resistance, it is easily thermally decomposed, and shrinkage or expansion due to heat may occur. Therefore, in order to prepare a flexible device, it is necessary to develop a polyimide that can maintain high transparency at high temperatures together with excellent mechanical characteristics and exhibit excellent thermal stability.

The present invention provides a polyfluorene imide precursor composition containing an acid dianhydride, a diamine, and a dimethyl siloxane (DMS) -diphenyl siloxane (DPS) oligomer represented by the following structural formula. And a solvent having a positive partition coefficient (LogP) at 25 ° C and a density of 1 g / cm ³ or less as polymerization components.

In the above structural formula, p and q are mole fractions. When p + q = 100, p is 70 to 90, and q is 10 to 30.

According to a preferred embodiment, the solvent may be an amidine solvent, specifically one selected from dimethylpropanamide (DMPA) or diethylpropanamide (DEPA).

Furthermore, a combination of N, N-diethylacetamide (DEAc), N, N-diethylformamide (DEF), One or more solvents of N-ethylpyrrolidone (NEP).

The polyfluorene imide copolymer of the present invention can reduce the number of flexible polyfluorene imine repeating structures and other polyfluorene imines due to the introduction of the structure of Chemical Formula 1 by using the organic solvent described above. Phenomenon caused by phase separation caused by polarity difference. Previously, two organic solvents were used in order to solve the above-mentioned phase separation, but the present invention can reduce the cloudiness phenomenon by using only one organic solvent, so that a more transparent polyimide film can be prepared.

In the present invention, a polyfluorene is prepared by polymerizing an acid dianhydride and a diamine in an organic solvent including a diamine having a higher molecular weight Si structure at a temperature of 25 ° C. and a positive logP and a density of 1 g / cm ³ or less. By this, imine can provide a polychromatic imide film which is more colorless and transparent, and which is excellent in heat resistance, that is, the thermal expansion and contraction behavior is relaxed.

According to an embodiment, the molecular weight of the diamine of Chemical Formula 1 may be 4000 g / mol or more, preferably it may have a molecular weight of 4400 g / mol or more, and more preferably 5000 g / mol or more. Here, the molecular weight refers to a weight average molecular weight, and the molecular weight can be calculated by an NMR analysis or a method of calculating an amine equivalent by an acid-base titration method.

When the molecular weight of the diamine including the structure of the above Chemical Formula 1 is less than 4000 g / mol, the heat resistance may decrease, for example, the glass transition temperature (Tg) of the prepared polyimide may decrease or the thermal expansion coefficient may be excessive. increase.

Furthermore, in Chemical Formula 1, p and q are Mohr fractions. When p + q = 100, p is 70 to 90 and q is 10 to 30. If p exceeds 90 and q is less than 10, they are compatible. Phase separation occurs due to deterioration in properties, and haze is produced in the prepared film due to the turbidity phenomenon of the precursor solution. When p is less than 70 and q exceeds 30, the effect of reducing the residual stress is reduced. [Chemical Formula 1]

According to an embodiment, more than one diamine may be used in the present invention. The overall diamine may include 1 mole% to 20 mole%, preferably 1 mole% to 10 mole%. Diamine.

According to an embodiment, the diamine of the above Chemical Formula 1 may be relative to the overall solid content of the polyfluorene imine copolymer, that is, the weight of the solid content of the polyfluorene imide precursor or the total of the polymerization components (diamine and acid dianhydride). It is 10 to 50% by weight, and preferably 10 to 40% by weight can be added. If the diamine including the structure of the above Chemical Formula 1 is excessively added to the total weight of the polymer, for example, 50% by weight or 40% by weight or more is added, the mechanical properties such as the modulus of the polyimide will decrease, The film strength is reduced, so physical damage such as film tearing will occur during the process. In addition, when a diamine having the structure of Chemical Formula 1 is excessively added, the glass transition temperature (Tg) derived from the polymer having the above-mentioned siloxane structure is exhibited, and thus at a low process temperature of 350 ° C or lower It exhibits glass transition temperature (Tg). During the inorganic film deposition process above 350 ° C, the surface of the film is wrinkled due to the phenomenon of polymer flow, which causes the phenomenon of cracking of the inorganic film.

FIG. 1 is a schematic view showing a structure of a copolymer prepared from a precursor composition of the present invention.

The present invention can increase the modulus strength of polyfluorene imine by inserting the structure of Chemical Formula 1 including a siloxane structure into the polyfluorene imine structure, and can alleviate the stress caused by external force. At this time, the polyfluorene imine including a siloxane structure may exhibit polarity, and phase separation may occur due to a difference in polarity from the polyfluorine imine structure not including a siloxane structure, so that the siloxane structure may be uneven. Ground distribution to the entire polyimide structure. In this case, it is not only difficult to show the effect of improving the physical properties such as the effect of increasing the strength of the polyimide and the effect of reducing the stress due to the siloxane structure, but also the haze due to phase separation is increased, so that the transparency of the film may be decline. In particular, in the case where the diamine including the siloxane structure has a high molecular weight, the polarity of the polyimide prepared therefrom becomes more obvious, and thus the phase separation phenomenon between polyimide is more apparent. . However, as shown in FIG. 1b, in the case of using a siloxane diamine having a low molecular weight structure, in order to exhibit effects such as stress relaxation, a larger amount needs to be added, which may occur at a lower temperature. Process problems such as glass transition temperature (Tg) will occur, so the physical properties of polyimide film will decrease. Therefore, when a high-molecular-weight siloxane diamine is added, as shown in FIG. 1b, a relaxation segment is largely formed in the molecule, so it can also be effective at a content less than the low-molecular-weight addition amount. The ground shows a stress relaxation effect. Therefore, the present invention studies a method for making the diamine of Chemical Formula 1 including the above-mentioned high-molecular weight siloxane structure more uniformly distributed on a polyimide matrix without phase separation.

In order to solve the above problems, there is also a method of mixing a polar solvent and a non-polar solvent. However, the polar solvent tends to have high volatility. Therefore, problems such as pre-volatilization may occur during the preparation process, so not only the reproducibility of the process will be produced. And other problems, and the problem of phase separation cannot be completely improved, so the haze of the prepared polyimide film will become high and the transparency will decrease. In the present invention, in order to uniformly distribute the polyfluorene imine structure including the structure of Chemical Formula 1 to the entire polyimide matrix, a solvent having a positive distribution coefficient (LogP) is used, and particularly a positive distribution coefficient (LogP) is used. Amine solvents, more specifically, by using a solvent including a solvent having an amphiphilic structure, not only can solve the process problems caused by the use of polar solvents, but also because of the amphiphilic molecular structure Even if only one kind of solvent is used, the polyimide can be uniformly distributed, so it is very suitable for solving the problem caused by phase separation, thereby providing a polyimide having significantly improved haze characteristics.

According to an embodiment, the tetracarboxylic dianhydride may be one selected from the group consisting of tetracarboxylic dianhydrides having a tetravalent organic group of the following chemical formula 2a to chemical formula 2h in a molecular structure. [Chemical Formula 2a] [Chemical Formula 2b] [Chemical Formula 2c] [Chemical Formula 2d] [Chemical Formula 2e] [Chemical Formula 2f] [Chemical Formula 2g] [Chemical Formula 2h]

In the above Chemical Formulas 2a to 2h, the above R ₁₁ to R ₂₄ may be each independently selected from a halogen atom including -F, -Cl, -Br, and -I, a hydroxyl group (-OH), and a thiol group (-SH ), Nitro (-NO ₂ ), cyano, alkyl having 1 to 10 carbon atoms, haloalkoxy having 1 to 4 carbon atoms, haloalkyl having 1 to 10 carbon atoms, carbon number Is a substituent in an aryl group of 6 to 20, the above a1 may be an integer of 0 to 2, a2 is an integer of 0 to 4, a3 is an integer of 0 to 8, and a4 and a5 are each independently an integer of 0 to 3 , A7 and a8 are independently integers from 0 to 3, a10 and a12 are independently integers from 0 to 3, a11 is an integer from 0 to 4, a15 and a16 are independently integers from 0 to 4, a17 and a16 are independently a18 is independently an integer from 0 to 4, a6, a9, a13, a14, a19, a20 are each independently an integer from 0 to 3, n is an integer from 1 to 3, and A ₁₁ to A ₁₆ may be independently Selected from -O-, -CR'R "-, -C (= O)-, -C (= O) O-, -C (= O) NH-, -S-, -SO _2- , benzene One of the groups consisting of a radical and a combination thereof, wherein the R 'and R "are each independently selected from the group consisting of a hydrogen atom and a carbon number of 1 to 10 One of the groups consisting of an alkyl group and a fluoroalkyl group having 1 to 10 carbon atoms.

In addition to the diamine of the above Chemical Formula 1, the present invention may include a diamine including 80 mol% to 99 mol% in the overall diamine content and containing a divalent organic group of the following Chemical Formula 3 in the molecular structure as a diamine. amine. [Chemical Formula 3]

In the above Chemical Formula 3, the R ₃₁ and R ₃₂ may be each independently selected from a halogen atom including -F, -Cl, -Br, and -I, a hydroxyl group (-OH), a thiol group (-SH), and a nitrate. (-NO ₂ ), cyano, alkyl having 1 to 10 carbon atoms, haloalkoxy having 1 to 4 carbon atoms, haloalkyl having 1 to 10 carbon atoms, and 6 to 6 carbon atoms The substituent in the aryl group of 20 is preferably a substituent selected from a halogen atom, a halogenated alkyl group, an alkyl group, an aryl group, and a cyano group. For example, the above halogen atom may be fluorine (-F), and the halogenated alkyl group may include a fluorine-based atom having 1 to 10 carbon atoms, and may be selected from a fluoromethyl group, a perfluoroethyl group, and a trifluoromethyl group. The alkyl group may be one selected from methyl, ethyl, propyl, isopropyl, third butyl, pentyl, and hexyl, and the aryl may be selected from phenyl, One of the naphthyl groups is more preferably a substituent containing a fluorine atom such as a fluorine atom and a fluoroalkyl group.

Q may be selected from a single bond, -O-, -CR'R "-, -C (= O)-, -C (= O) O-, -C (= O) NH-, -S-,- One of the groups consisting of SO _2- , phenylene, and combinations thereof, at this time, the above R 'and R "are each independently selected from a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and a carbon number One of the groups consisting of 1 to 10 fluoroalkyl groups.

Here, the "fluorine-based substituent" in the present invention means not only a "fluorine-based substituent" but also a "fluorine-containing substituent".

Specifically, the diamine of the above Chemical Formula 3 may be one selected from the compounds represented by the following Chemical Formulas 3a to 3d.

In the above Chemical Formulas 3a to 3d, Q is the same as described above.

According to an embodiment, the above tetracarboxylic dianhydride may include 20 mol% to 80 mol%, preferably 30 mol% to 80 mol%, and more preferably 30 mol in the overall tetracarboxylic dianhydride. % To 70 mol% of a tetracarboxylic dianhydride containing a structure of the following Chemical Formula 4. [Chemical Formula 4]

According to an embodiment, the above tetracarboxylic dianhydride may include 20 mol% to 80 mol%, preferably 20 mol% to 60 mol%, and more preferably 20 mol in the overall tetracarboxylic dianhydride. % To 50 mol% of a tetracarboxylic dianhydride containing a structure of the following Chemical Formula 5. [Chemical Formula 5]

In the above Chemical Formula 5, Q ₁ and Q ₂ are each independently selected from a single bond, -O-, -C (= O)-, -C (= O) O-, -C (= O) NH-, One of the groups consisting of -S-, -SO _2- , phenylene, and combinations thereof.

According to an embodiment, the aforementioned chemical formula 5 may be a compound of the following chemical formula 5a to 5e.

The phase difference in the thickness direction of the film can be reduced by including a repeating structure including the fluorene structure in the polyfluoreneimine structure.

In the present invention, one or more types of tetracarboxylic dianhydride selected from a tetravalent organic group structure including the following chemical formula 6a to chemical formula 6r may be used together with the tetracarboxylic dianhydride of Chemical Formula 4 or Chemical Formula 5.

In the above 6l, A ₂ may be selected from a single bond, -O-, -C (= O)-, -C (= O) NH-, -S-, -SO _2- , phenylene, and combinations thereof. In one of the formed groups, v is an integer of 0 or 1, and in the above 6r, x is an integer of 1 to 10.

In addition, one or more hydrogen atoms in the tetravalent organic groups of 6a to 6r may be selected from halogen atoms including -F, -Cl, -Br, and -I, a hydroxyl group (-OH), and a thiol. (-SH), nitro (-NO ₂ ), cyano, alkyl having 1 to 10 carbon atoms, haloalkoxy having 1 to 4 carbon atoms, haloalkyl having 1 to 10 carbon atoms 2. Substituting the substituent in the aryl group having 6 to 20 carbon atoms.

Alternatively, in the present invention, the tetracarboxylic dianhydrides of Chemical Formula 4 and Chemical Formula 5 may be used together, and when the tetracarboxylic dianhydrides of Chemical Formula 4 and Chemical Formula 5 are used together, compared with the tetracarboxylic dianhydride described above, The total content of the anhydride may include the content of 10 to 30 mol%, preferably 10 to 25 mol%, and more preferably 15 to 25 mol%. Carboxylic dianhydride. The compound of Chemical Formula 5 including the above-mentioned fluorene structure and the compound represented by Chemical Formula 4 are used together to prepare polyfluorene imine, thereby reducing the surface shrinkage characteristics due to heat, which can improve the generation during cooling process after heating process. The film shrinks and improves heat resistance such as glass transition temperature.

According to an embodiment of the present invention, the total content of the tetracarboxylic dianhydride and the content of the diamine can be reacted at a molar ratio of 1: 1.1 to 1.1: 1. In order to improve reactivity and processability, it is preferred to The reaction is carried out such that the total content of the tetracarboxylic dianhydride is more than the diamine, or the reaction is carried out such that the content of the diamine is more than the total content of the tetracarboxylic dianhydride.

According to an embodiment of the present invention, preferably, the total content of the tetracarboxylic dianhydride and the content of the diamine can be performed at a molar ratio of 1: 0.99 to 0.99: 1, preferably 1: 0.98 to 0.98: 1. reaction.

Further, as the organic solvent that can be used for the above-mentioned polymerization reaction, a partition coefficient (LogP value) at 25 ° C is a positive number, a boiling point is 180 ° C or less, and a density is 1 g / cm ³ or less, more specifically, In other words, the value of the distribution coefficient (LogP) can be 0.01 to 3, 0.1 to 2, or 0.5 to 1.5. The partition coefficients of dimethylpropanamide (DMPA) and diethylpropanamide (DEPA) are 0.504 and 1.275, respectively, and the density is about 0.876 g / cm ³ and 0.870 g / cm ³ .

The above distribution coefficients can be calculated using the ACD / LogP module of the ACD / Labs company's ACD / Percepta platform. The ACD / LogP module uses the two-dimensional structure of the molecule and uses the quantitative structural property relationship (Quantitative Structure). -Property Relationship (QSPR) methodological algorithm.

In the case where the above-mentioned partition coefficient value is positive, it means that the polarity of the solvent is hydrophobic. According to the research by the inventors, it can be known that if a specific solvent with a positive partition coefficient is used to prepare the polyimide precursor composition, Then, the curling characteristics of the solution are improved. Furthermore, as described above, the present invention uses a solvent having a positive coefficient of distribution (LogP), and therefore has the effect of controlling the surface tension of the material and the smoothness of the coating film without using an additive such as a leveling agent, which can be controlled. The liquid curl phenomenon of the solution, because no additional additives such as additives are used, can not only eliminate the quality and process problems of containing low molecular substances in the final product, but also form a polyimide film with uniform characteristics more efficiently. .

For example, in the process of applying a polyimide precursor composition to a glass substrate, when the coating liquid is placed during hardening or under a humidity condition, a solution curl phenomenon due to shrinkage of the coating layer may occur. Such a liquid curling phenomenon of the coating solution may cause a deviation in the thickness of the film, thereby causing insufficient bending resistance of the film, which may cause the film to break or the corners to break during cutting. Therefore, the workability in the manufacturing process is poor and The problem of reduced yield.

In addition, when a polar foreign substance flows into a polyimide precursor composition coated on a substrate, a polyimide precursor composition including a polar solvent having a negative partition coefficient (LogP) may result. Due to the polarity of the foreign matter, cracks or thickness changes of the coating occur locally based on the position of the foreign matter. However, even when a hydrophobic solvent with a positive partition coefficient (LogP) is used, even small polar flows Foreign matter can also reduce or suppress thickness changes caused by cracks in the coating.

Specifically, a polyimide precursor composition including a solvent having a positive partition coefficient (LogP) may have a dewetting ratio defined by the following Formula 1 of 0% to 0.1% or less.

[Formula 1] Curling rate (%) = [(A-B) / A] × 100

In the above formula 1, A: the area in a state where the polyfluorene imide precursor composition is completely coated on the substrate (100 mm × 100 mm), and B: self-coated with the polyfluorene imide precursor composition or The area after the edge of the substrate of the PI film is curled.

The liquid dewetting phenomenon of the polyimide precursor composition and the film may occur within 30 minutes after the polyimide precursor composition solution is applied, and especially it starts to roll up from the edges, so it will be thicker. The thickness of the formed edges.

After the polyimide precursor composition of the present invention is applied to a substrate, the applied resin composition is left for 10 minutes or longer (for example, under a humidity condition for 10 minutes or longer, such as 40 minutes or longer). The curling rate of the material solution may be 0.1% or less, for example, at a temperature of 20 ° C to 30 ° C, under a humidity condition of 40% or more, more specifically, a humidity condition in a range of 40% to 80% (that is, 50%, 60%, 70%, 80% of each humidity condition), for example, after being left for 10 minutes to 50 minutes under 50% humidity conditions, it can also show a very small curl rate of less than 0.1%, preferably it can be It exhibited a curl rate of 0.05%, more preferably almost 0%.

The curling rate as described above is also maintained after hardening. For example, after the polyimide precursor composition is applied to a substrate, it is left for more than 10 minutes, for example, at a temperature of 20 ° C to 30 ° C at 40% or more. Humidity conditions, more specifically, humidity conditions in the range of 40% to 80% (ie, humidity conditions of 40%, 50%, 60%, 70%, 80%), for example, placed at 50% humidity conditions for 10 After 15 minutes to 50 minutes, the curl rate of the cured polyimide film can be 0.1% or less, that is, in the hardening process by heat treatment, there is almost no curl or no curl. Specifically, it can express A curl rate of 0.05%, more preferably almost close to 0%.

The polyfluorene imide precursor composition of the present invention can obtain a polyfluorene imide film with more uniform characteristics by solving such a liquid curl phenomenon, thereby further improving the yield of the preparation process.

In addition, the density of the solvent of the present invention can be measured by a standard measurement method of American Society for Testing Materials (ASTM) D1475. The density may be 1 g / cm ³ or less, and the density may be 1 g / cm ³ . When the value is greater than cm ³ , the relative viscosity becomes high, and the process efficiency decreases.

The method for reacting the above tetracarboxylic dianhydride with a diamine can be implemented according to a typical polymerization preparation method of a polyimide precursor (such as solution polymerization). Specifically, the method can be prepared by dissolving the diamine in After being in an organic solvent, tetracarboxylic dianhydride was added to the obtained mixed solution to perform a polymerization reaction.

According to an embodiment, the polymerization may be performed by a method including the following steps: a) a step of feeding the diamine of the above chemical formula 1 into an organic solvent; b) a diamine of the chemical formula 3 into the step prepared in the step a) A solution step; c) a step of adding more than one tetracarboxylic dianhydride to the solution prepared in step b) above; and d) a step of polymerizing the solution prepared in step c) above at a specific reaction temperature .

The above reaction can be performed under an inert gas or nitrogen gas stream, and can be performed under anhydrous conditions.

The polymerization reaction may be carried out at a reaction temperature of -20 ° C to 80 ° C, preferably 0 ° C to 80 ° C. When the reaction temperature is too high, the reactivity becomes high and the molecular weight becomes large, and the viscosity of the precursor composition increases, which is disadvantageous in the manufacturing process.

In consideration of processability such as coatability during the film formation process, the polyimide precursor composition prepared according to the above-mentioned production method preferably includes a solid component in an amount capable of providing the composition with an appropriate viscosity. According to an embodiment, it can be adjusted so that the content of the whole polyimide precursor becomes 8 to 25% by weight, preferably 10 to 25% by weight, and more preferably 10 to 20% by weight. The content of the composition.

Optionally, the polyimide precursor composition may be adjusted to have a viscosity of 3,000 cP or more or 4,000 cP or more. The viscosity of the polyimide precursor composition is preferably 10,000 cP or less, The viscosity is preferably adjusted to 9,000 cP or less, and more preferably 8,000 cP or less. When the viscosity of the polyimide precursor composition exceeds 10,000 cP, when the polyimide film is processed, the defoaming efficiency is reduced, so not only the process efficiency is reduced, but also the prepared film may be affected by bubbles. This results in poor surface roughness, which reduces electrical, optical, and mechanical properties.

Furthermore, the molecular weight of the polyimide of the present invention may have a weight average molecular weight of 10,000 g / mol to 200,000 g / mol, 20,000 g / mol to 100,000 g / mol, or 30,000 g / mol to 100,000 g / mol. The molecular weight distribution (Mw / Mn) of the polyfluorene imine of the present invention is preferably 1.1 to 2.5. When the weight average molecular weight or molecular weight distribution of the polyfluorene imide deviates from the above range, there is a concern that it is difficult to form a film, or the characteristics of the polyfluorene imide film such as transmittance, heat resistance, and mechanical properties are reduced.

Next, the polyfluorene imide precursor obtained after the polymerization reaction is fluorinated, whereby a transparent polyfluorene imide film can be prepared. At this time, specifically, the aforementioned fluorene imidization process may include a chemical fluorene imidization method or a thermal fluorene imidization method.

For example, polyimide can be obtained by adding a dehydrating agent and an imidization catalyst to the polymerized polyimide precursor composition, followed by heating at a temperature of 50 ° C to 100 ° C. The amidine imidization is performed by a chemical reaction, or the above solution is refluxed and the alcohol is removed simultaneously.

In the above chemical fluorene imidization method, pyridine, triethylamine, methylpyridine, or quinoline can be used as the fluorene imidization catalyst. In addition, there are substituted or unsubstituted nitrogen-containing heterocycles. Ring compounds, N-oxide compounds of nitrogen-containing heterocyclic compounds, substituted or unsubstituted amino acid compounds, aromatic hydrocarbon compounds having a hydroxyl group or aromatic heterocyclic compounds, and in particular, 1,2 can also be used -Derived from imidazole such as dimethylimidazole, N-methylimidazole, N-benzyl-2-methylimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 5-methylbenzimidazole, etc. Substance, isoquinoline, 3,5-dimethylpyridine, 3,4-dimethylpyridine, 2,5-dimethylpyridine, 2,4-dimethylpyridine, 4-n-propylpyridine, etc. Pyridine, p-toluenesulfonic acid and the like.

An acid anhydride such as acetic anhydride can be used as the above-mentioned dehydrating agent.

Alternatively, the imidization may be performed by a method in which the polyimide precursor composition is coated on the substrate and then heat-treated.

The above polyfluorene imide precursor composition may be in the form of a solution dissolved in an organic solvent, and in such a case, or when the polyfluorine imide precursor is synthesized in an organic solvent, the solution may be The obtained reaction solution itself may be one obtained by diluting the reaction solution with another solvent. When the polyimide precursor is obtained as a powder, the solution may be a solution prepared by dissolving the powder in an organic solvent.

The invention provides a method for preparing a polyfluorene imide film, comprising: a step of coating the polyfluorine imide precursor composition on a substrate; and performing the coating on the polyfluorine imide precursor composition. Steps of heat treatment.

The above polyfluorene imide precursor composition is coated on a substrate, and heat treatment is performed in an infrared (IR) oven, a hot air oven, or a hot plate. At this time, the heat treatment temperature may be 300 ° C to 500 ° C, preferably The temperature range is from 320 ° C to 480 ° C, and the heat treatment can also be performed in multiple steps within the above temperature range. The heat treatment process can be performed for 20 minutes to 70 minutes, and preferably for about 20 minutes to 60 minutes.

As the organic solvent contained in the polyfluorene imide precursor composition of the present invention, the same organic solvent as used in the above-mentioned synthesis reaction can be used.

As long as the effect is not impaired, the present invention may also include a silane coupling agent, a crosslinkable compound, and a fluorene imidation accelerator for the purpose of efficiently performing fluorimidization.

In addition, the haze of the polyimide film may have a haze value of 2 or less, preferably 1 or less, or 0.9 or less, so that a polyimide film having improved transparency can be provided. At this time, the thickness of the polyamide film may be 8 μm to 15 μm, and preferably 10 μm to 12 μm.

In addition, it may be a colorless and transparent polyimide film: within a film thickness range of 5 μm to 30 μm, the transmittance of light at a wavelength of 380 nm to 760 nm is 80% or more, and the yellowness (YI) is About 15 or less, preferably about 10 or less, and more preferably about 8 or less. Since it has excellent light transmittance and yellowness as described above, it can exhibit significantly improved transparency and optical characteristics.

In addition, the in-plane retardation value (R _in ) of the polyfluorene-imide-based film may be about 0 nm to 100 nm, and the retardation value (R _th ) in the thickness direction may be less than about 1000 nm or 0 nm to 700 nm. , Preferably 0 nm to 600 nm, and more preferably 0 nm to 500 nm. Within the range of the phase difference in the thickness direction, the visual sensitivity suitable for a display can be exhibited. When the phase difference in the thickness direction is 1000 nm or more, a phase difference occurs in the polyimide film and the light is distorted. Visual sensitivity will be significantly reduced.

The glass transition temperature (Tg) of the polyfluoreneimide film of the present invention may be 350 ° C or higher, preferably 360 ° C or higher, and more preferably 370 ° C or higher.

Furthermore, the thermal stability of the polyimide film according to the present invention corresponding to temperature changes may be excellent, for example, the thermal expansion coefficient after n + 1 heating and cooling processes in a temperature range of 100 ° C to 400 ° C. It may have a value of -10 ppm / ° C to 100 ppm / ° C, preferably -7 ppm / ° C to 90 ppm / ° C, and more preferably 80 ppm / ° C or less.

In still another embodiment of the present invention, an article including the polyfluorene imine copolymer is provided.

The molded article may be a film, a fiber, a coating material, an adhesive material, and the like, but is not limited thereto. The molded article may be formed by a dry-wet method, a dry method, a wet method, or the like using the complex composition of the copolymer and inorganic particles, but is not limited thereto. Specifically, the molded article may be an optical film as described above. In this case, the composition including the polyfluorene imine copolymer can be easily prepared by applying it to a method such as spin coating, etc. After being on the substrate, it is dried and hardened.

The polyimide of the present invention can maintain characteristics such as heat resistance, mechanical strength, and the like due to a strong structure. In particular, the polyimide not only exhibits excellent heat resistance against heat shrinkage behavior that may occur during a high-temperature process, but also exhibits Excellent colorless and transparent characteristics, so it can be used in, for example, element substrates, cover substrates for displays, optical films, integrated circuit (IC) packages, adhesive films, and multilayer FPC (flexible printed circuit) , Tape, touch panel, protective film for optical discs, etc.

According to still another embodiment of the present invention, a display device including the above-mentioned molded article is provided. Specifically, the display device may include a liquid crystal display device (LCD), an organic light emitting diode (OLED), and the like. In particular, the display device may be suitable for use of low-temperature polycrystalline silicon (low temperature) that requires a high-temperature process. temperature polycrystalline silicon (LTPS) process, but it is not limited to this.

Hereinafter, embodiments of the present invention will be described in detail so that a person having ordinary knowledge in the technical field to which the present invention pertains can easily implement. However, the present invention can be implemented in many different forms, and is not limited to the embodiments described herein.

<Example 1>

164 g of dimethylpropanamide (DMPA) (partition coefficient: 0.504) was filled in a stirrer flowing a nitrogen gas stream, and then the temperature of the reactor was maintained at 25 ° C, and then added at the same temperature. 0.0017 mol of two-terminated amine modified DMS-DPS (molecular weight 5000 g / mol) and 0.0518 mol of 2,2'-bis (trifluoromethyl) -4,4'-biphenyldiamine (2, 2'-bis (trifluoromethyl) benzidine (TFMB). At the same temperature, 0.0321 mol of Pyromellitic Dianhydride (PMDA) and 0.0214 mol of 9,9'-bis (3,4-dicarboxybenzene) were added to the solution to which the above DMS-DPS and TFMB were added. Base) fluorinated dianhydride (9,9'-bis (3,4-dicaroxyphenyl) fluorene dianhydride, BPAF) and stirred for 3 hours, and then stirred at 80 ° C for 4 hours to prepare a precursor composition.

The NMR analysis results of DMS-DPS used in Example 1 are shown in FIG. 2. In the DMS-DPS structure of Chemical Formula 1, p = 73.3, q = 26.7.

<Example 2>

Fill 100 g of diethylpropanamide (DEPA) (partition coefficient: 1.275) as a solvent in a stirrer flowing a nitrogen gas stream, and then keep the temperature of the reactor at 25 ° C at the same temperature Next, 0.0014 mol of two capped amine modified DMS-DPS (molecular weight of 5000 g / mol) and 0.0306 mol of TFMB (2,2'-bis (trifluoromethyl) benzidine) were added to dissolve. At the same temperature, 0.03211 mol of PMDA (Pyromellitic Dianhydride) was added to the solution to which the above DMS-DPS and TFMB were added, followed by stirring for 3 hours, and then stirring at 80 ° C for 4 hours.

〈Comparative example 1〉

Fill a stirrer flowing nitrogen gas with 96 g of N-Methylpyrrolidone (NMP) (partition coefficient: -0.28), and then keep the temperature of the reactor at 25 ° C in the same state At the temperature of 0.0017 mol, two blocked amine modified DMS-DPS (Diphenylsiloxane-dimethylsiloxane co-oligomer) with a molecular weight of 4400 g / mol, p = 95.2, q = 4.8) and 0.0304 mol of TFMB (2,2'-bis (trifluoromethyl) benzidine). 0.0321 mol of PMDA (Pyromellitic Dianhydride) was added to the solution to which the above-mentioned DMS-DPS and TFMB were added at the same temperature, and the mixture was stirred for 3 hours, and then stirred at 80 ° C for 4 hours.

〈Comparative example 2〉

137 g of NMP (partition coefficient -0.28) was filled in a stirrer flowing a nitrogen gas stream, and then, while the temperature of the reactor was maintained at 25 ° C, 0.0014 mol of two-terminal amine groups were added at the same temperature. DMS-DPS (with a molecular weight of 5000 g / mol, p = 50.8, q = 49.2) and 0.0306 mol of TFMB (2,2'-bis (trifluoromethyl) benzidine). At the same temperature, 0.03211 mol of PMDA (Pyromellitic Dianhydride) was added to the solution to which the above-mentioned DMS-DPS and TFMB were added and stirred for 3 hours, and then stirred at 80 ° C for 4 hours.

＜ Preparation example ＞

The polyimide copolymers prepared in the above-mentioned Examples 1 to 2 and Comparative Examples 1 to 2 were spin-coated on a glass substrate with a thickness of 9.5 μm to 11 μm. The glass substrate coated with the polyfluorene imide copolymer was placed in an oven and heated at a rate of 2 ° C / min, and was held at 80 ° C for 15 minutes, at 150 ° C for 30 minutes, and at 220 ° C for 30 minutes. The hardening process was performed by holding at 400 ° C. for 1 hour. After the hardening process was completed, the glass substrate was immersed in water to peel off the film formed on the glass substrate, and then dried in an oven at 100 ° C. to prepare a polyimide film.

The yellowness (YI), haze, phase difference in the thickness direction, CTE, glass transition temperature (Tg), and glass stress (bow) of the prepared polyimide film were measured and shown in Table 1. .

＜ Yellowness （YI） ＞

Color Eye 7000A was used to measure the yellowness (YI).

<Haze>

The haze was measured by a method of ASTM D1003 using a Haze Meter HM-150.

<Phase difference in thickness direction>

The phase difference (R _th ) in the thickness direction was measured by Axoscan. After the film was cut into a fixed size to measure the thickness, the phase difference was measured by Axoscan, and the measured thickness was inputted in a C-plate direction to compensate for the phase difference value.

＜ Coefficient of thermal expansion (CTE) and glass transition temperature (Tg) ＞

After preparing the above-mentioned film in a size of 5 mm × 20 mm, a sample was loaded with an accessory. The actual measured film length was uniformly 16 mm. The tensile force of the stretched film was set to 0.02 N, and the temperature rising process was performed once at a temperature rising rate of 5 ° C / min in a temperature range of 100 ° C to 350 ° C, and then a Thermo Mechanical Analyzer (TMA) (TA The company's Q400) measures the change in thermal expansion when cooling is performed at a cooling rate of 4 ° C / min in a temperature range of 350 ° C to 100 ° C.

At this time, the glass transition temperature (Tg) is used to indicate the inflection point exhibited in the temperature increase interval during the primary temperature increase process.

＜ Glass stress ＞

The glass stress is expressed as a bow value, and the measurement method is as follows.

A 10 cm × 10 cm glass was set to a stress tester (FLX2320 from Tencor Corporation), and after scanning the center with a laser, the center portion of a total of 8 cm except 1 cm on both sides was moved to the left and right sides by 4 cm. The distance (height) deviation of the glass is measured.

[Table 1]

According to Table 1, it can be seen that the polyfluorene imine copolymers of Examples 1 to 2 use the DMS-DPS with a DMS-DPS block having a molar ratio of 73.3: 26.7 without solution turbidity and haze characteristics of the film improve. On the contrary, the ratio of the DMS block of Comparative Example 1 was high, the solution became cloudy, and the haze of the film was also poor. Furthermore, it can be seen that when the ratio of the DPS block is relatively high as in Comparative Example 2, a high residual stress is exhibited.

Furthermore, it can be seen that the optical properties and heat resistance of Examples 1 and 2 are improved compared to Comparative Example 1 by using a solvent having a positive distribution coefficient (LogP) and a density of 1 g / cm ³ or less.

In the foregoing, specific parts of the content of the present invention have been described in detail. Those skilled in the art should understand that such specific descriptions are only preferred embodiments, and the scope of the present invention is not limited thereto. Therefore, the substantial scope of the present invention is defined by the scope of the accompanying invention application patent and its equivalent.

no

FIG. 1 is a schematic diagram for explaining a structure of a copolymer prepared from a precursor composition of the present invention. FIG. 2 is a nuclear magnetic resonance (NMR) analysis result of the DMS-DPS oligomer used in Example 1. FIG.

Claims (15)

A polyimide precursor composition comprising an acid dianhydride, a diamine, a dimethylsilane-diphenylsilane oligomer represented by the following structural formula, and a partition coefficient at 25 ° C As a polymerization component, a solvent having a positive number and a density of 1 g / cm ³ or less: In the structural formula, p and q are mole fractions. When p + q = 100, p is 70 to 90, and q is 10 to 30. The polyimide precursor composition according to item 1 of the scope of the patent application, wherein the solvent is a fluorene-based solvent. The polyimide precursor composition according to item 2 of the scope of the patent application, wherein the fluorene-based solvent is dimethylpropylamine or diethylpropylamine. The polyimide precursor composition according to item 1 of the scope of the patent application, wherein the molecular weight of the dimethylsiloxane-diphenylsiloxane oligomer is 4,000 g / mol or more. The polyimide precursor composition according to item 1 of the scope of the patent application, wherein the acid dianhydride is a tetracarboxylic acid selected from a molecular structure including a tetravalent organic group of the following chemical formula 2a to chemical formula 2h One or more of dianhydrides: [Chemical Formula 2a] [Chemical Formula 2b] [Chemical Formula 2c] [Chemical Formula 2d] [Chemical Formula 2e] [Chemical Formula 2f] [Chemical Formula 2g] [Chemical Formula 2h] In the chemical formula 2a to the chemical formula 2h, R ₁₁ to R ₂₄ are each independently selected from a halogen atom including -F, -Cl, -Br, and -I, a hydroxyl group (-OH), and a thiol group (- SH), nitro (-NO ₂ ), cyano, alkyl having 1 to 10 carbon atoms, haloalkoxy having 1 to 4 carbon atoms, haloalkyl having 1 to 10 carbon atoms, or carbon atom Substituents in aryl groups of 6 to 20, where a1 may be an integer from 0 to 2, a2 is an integer from 0 to 4, a3 is an integer from 0 to 8, and a4 and a5 are each independently 0 to 3 Integers, a7 and a8 are independently integers from 0 to 3, a10 and a12 are independently integers from 0 to 3, a11 is an integer from 0 to 4, a15 and a16 are independently integers from 0 to 4, and a17 And a18 are each independently an integer from 0 to 4, a6, a9, a13, a14, a19, and a20 are each independently an integer from 0 to 3, n is an integer from 1 to 3, and A ₁₁ to A ₁₆ are each independently Selected from -O-, -CR'R "-, -C (= O)-, -C (= O) O-, -C (= O) NH-, -S-, -SO _2- , benzene One of a group consisting of a radical and a combination thereof, wherein R ′ and R ″ are each independently selected from an alkyl group having a hydrogen atom and a carbon number of 1 to 10 And a fluoroalkyl group having 1 to 10 carbon atoms. The polyfluorene imide precursor composition according to item 1 of the scope of patent application, wherein the diamine includes a diamine containing a divalent organic group of the following Chemical Formula 3 in a molecular structure: [Chemical Formula 3] In the chemical formula 3, R ₃₁ and R ₃₂ are each independently selected from a halogen atom including -F, -Cl, -Br, and -I, a hydroxyl group (-OH), a thiol group (-SH), and a nitro group. (-NO ₂ ), cyano, alkyl having 1 to 10 carbon atoms, haloalkoxy having 1 to 4 carbon atoms, haloalkyl having 1 to 10 carbon atoms, and 6 to 20 carbon atoms A substituent in the aryl group, Q is selected from the group consisting of a single bond, -O-, -CR'R "-, -C (= O)-, -C (= O) O-, -C (= O) NH One of the groups consisting of-, -S-, -SO _2- , phenylene, and combinations thereof, at this time R 'and R "are independently selected from the group consisting of a hydrogen atom and a carbon number of 1 to 10 One of the group consisting of an alkyl group and a fluoroalkyl group having 1 to 10 carbon atoms. The polyfluorene imide precursor composition according to item 1 of the scope of patent application, wherein the acid dianhydride includes 20 mol% to 80 mol% of the total tetracarboxylic dianhydride and contains the following chemical formula 4 Structure of tetracarboxylic dianhydride: [Chemical Formula 4] . The polyfluorene imide precursor composition according to item 1 of the scope of the patent application, wherein the acid dianhydride includes 20 mol% to 80 mol% of the tetracarboxylic dianhydride in the following formula 5 Carboxylic dianhydride: [Chemical Formula 5] In the chemical formula 5, Q ₁ and Q ₂ are each independently selected from a single bond, -O-, -C (= O)-, -C (= O) O-, -C (= O) NH- One of the groups consisting of-, -S-, -SO _2- , phenylene, and combinations thereof. The polyimide precursor composition according to item 1 of the scope of the patent application, wherein the acid dianhydride includes the following tetracarboxylic dianhydrides of Chemical Formula 4 and Chemical Formula 5: [Chemical Formula 4] [Chemical Formula 5] In the chemical formula 5, Q ₁ and Q ₂ are each independently selected from a single bond, -O-, -C (= O)-, -C (= O) O-, -C (= O) NH- One of the groups consisting of-, -S-, -SO _2- , phenylene, and combinations thereof. A polyimide film is prepared from the polyimide precursor composition according to any one of claims 1 to 9 of the scope of patent application. The polyfluorene imide film according to item 10 of the scope of application for a patent, wherein the haze of the polyfluorene imide film is 2 or less. The polyimide film according to item 10 of the scope of application patent, wherein the glass transition temperature of the polyimide film is 350 ° C. or higher. The polyfluorene imide film according to item 10 of the scope of application for a patent, wherein the thermal expansion coefficient of the polyfluorene imide film is 100 ppm / ° C or lower. A transparent polyimide substrate for an oxide thin film transistor, which is prepared from the polyimide precursor composition according to any one of claims 1 to 9 of the scope of patent application. A transparent polyimide substrate for low-temperature polycrystalline silicon is prepared from the polyimide precursor composition according to any one of claims 1 to 9 of the scope of application for a patent.